Environmental Ellipsometric Porosimetry Research Articles

Multilevel effective material approximation for modeling ellipsometric measurements on complex porous thin films

Abstract Catalysts are important components in chemical processes because they lower the activation energy and thus determine the rate, efficiency and selectivity of a chemical reaction. This property plays an important role in many of today’s processes, including the electrochemical splitting of water. Due to the continuous development of catalyst materials, they are becoming more complex, which makes a reliable evaluation of physicochemical properties challenging even for modern analytical measurement techniques and industrial manufacturing. We present a fast, vacuum-free and non-destructive analytical approach using multi-sample spectroscopic ellipsometry to determine relevant material parameters such as film thickness, porosity and composition of mesoporous IrOx–TiOy films. Mesoporous IrOx–TiOy films were deposited on Si wafers by sol–gel synthesis, varying the composition of the mixed oxide films between 0 and 100 wt%Ir. The ellipsometric modeling is based on an anisotropic Bruggeman effective medium approximation (a-BEMA) to determine the film thickness and volume fraction of the material and pores. The volume fraction of the material was again modeled using a Bruggeman EMA to determine the chemical composition of the materials. The ellipsometric fitting results were compared with complementary methods, such as scanning electron microscopy (SEM), electron probe microanalysis (EPMA) as well as environmental ellipsometric porosimetry (EEP).

Interparticle Forces of a Native and Encapsulated Metal-Organic Framework and Their Effects on Colloidal Dispersion.

The colloidal properties of suspended metal-organic frameworks (MOFs) are critical for device fabrication and application. Herein, van der Waals attractive, electric double layer repulsive, and steric repulsive forces of a native and encapsulated MOF are quantified for the first time. The van der Waals attractive forces were investigated by conducting environmental ellipsometric porosimetry (EEP) and spectroscopic ellipsometry (SE) on submicron, optical-quality nanoparticle films. The repulsive forces were determined from colloid and material characterization measurements. These data were used to predict suspension properties via extended Derjaguin, Landau, Verwey, and Overbeek theory. The state of dispersion was quantified for comparison with theoretical predictions for nine solvents. The MOF encapsulated with a surface-selective modification showed superior suspension in hydrophobic solvents. These findings should expedite the formulation of MOF colloidal suspensions for future works.

Bimodal Porosity and Stability of a TiO2 Gig-Lox Sponge Infiltrated with Methyl-Ammonium Lead Iodide Perovskite.

We created a blend between a TiO2 sponge with bimodal porosity and a Methyl-Ammonium Lead Iodide (MAPbI3) perovskite. The interpenetration of the two materials is effective thanks to the peculiar sponge structure. During the early stages of the growth of the TiO2 sponge, the formation of 5–10 nm-large TiO2 auto-seeds is observed which set the micro-porosity (<5 nm) of the layer, maintained during further growth. In a second stage, the auto-seeds aggregate into hundreds-of-nm-large meso-structures by their mutual shadowing of the grazing Ti flux for local oxidation. This process generates meso-pores (10–100 nm) treading across the growing layer, as accessed by tomographic synchrotron radiation coherent X-ray imaging and environmental ellipsometric porosimetry. The distributions of pore size are extracted before (>47% V) and after MAPbI3 loading, and after blend ageing, unfolding a starting pore filling above 80% in volume. The degradation of the perovskite in the blend follows a standard path towards PbI2 accompanied by the concomitant release of volatile species, with an activation energy of 0.87 eV under humid air. The use of dry nitrogen as environmental condition has a positive impact in increasing this energy by ~0.1 eV that extends the half-life of the material to 7 months under continuous operation at 60 °C.

Broadband antireflective coating stack based on mesoporous silica by acid-catalyzed sol-gel method for concentrated photovoltaic application

Silica multi-layer stacks have been designed with the aim to provide broadband antireflective (AR) properties for glass components in concentrated photovoltaic (CPV) application. Silica porous coatings were grown by combining acid-catalyzed sol-gel route and evaporation induced self-assembly (EISA) method with four types of organic/inorganic systems. Sols were prepared using tetraethylorthosilicate (TEOS) as inorganic precursor assembled with two di-block copolymers, one tri-block copolymer and one cationic surfactant as organic templates. Optical properties were characterized by ellipsometry and spectrophotometry while the material structure was analyzed by environmental ellipsometric porosimetry (EEP) and atomic force microscopy (AFM). The concentration of inorganic and organic phases was optimized and a broadband AR bi-layer stack was obtained providing a 7.2% (under the reference AM1.5 solar spectral irradiance) increase in transmittance over bare glass in the wavelength range 300–2000 nm when coated on both sides.

Improving the Selective Efficiency of Graphene-Mediated Enhanced Raman Scattering through Molecular Imprinting.

Enhancement of Raman scattering signal through graphene is an important property that could be exploited for producing innovative sensing devices with advanced properties. Because the enhancement of Raman scattering is due to only a chemical mechanism, the amplification of the signal is lower than that one produced by excitation of localized surface plasmons. The combination of a highly selective technique, which is molecular imprinting, with graphene-mediated enhanced Raman scattering, represents a new synergistic approach that we have developed in the present work. The careful material design has allowed obtaining a porous composite embedding exfoliated graphene and molecular cavities specifically designed for recognizing Rhodamine 6G. The molecularly imprinted porous samples have shown a signal enhancement that increases as a function of the number of molecular cavities, which are also accountable for the molecular recognition properties. Environmental ellipsometric porosimetry has shown no substantial difference between molecularly imprinted and not-imprinted films confirming that the signal enhancement of the imprinted samples is due to the molecular cavities. Interestingly, the most efficient sample has shown a Raman enhancement per cavity that exceeds the value of 1 × 1012 and a remarkable molecular selectivity allowing for a Rhodamine 6G signal amplification 4.5 higher than structural analogues such as Rhodamine B and methylene blue. The robust and flexible matrix ensures a good recyclability of the samples without lack of linear response. These results prove the great potential of molecular imprinting as a general strategy to provide selectivity to GERS-active substrates for a new generation of sensing devices.

Ca doping of mesoporous TiO2 films for enhanced photocatalytic efficiency under solar irradiation

Anatase mesoporous TiO2 films doped with Ca were prepared by sol–gel and deposited onto glass slides. The influence of the dopant in the textural and structural properties of the films was studied together with their photocatalytic activity. Titania sols w/o and with Ca were synthesised from titanium isopropoxide as TiO2 precursor, acetic acid as complexing agent, and polyethylene glycol hexadecyl ether (Brij58) as pore-generating agent. The TiO2 films were characterised by Fourier transform infrared spectroscopy, Raman spectroscopy, and transmission electron microscopy. Environmental ellipsometric porosimetry was used to obtain the adsorption–desorption isotherms and the total pore volume, for determining the pore size distribution and specific surface area (S s) of the films, crucial parameters that govern the photocatalytic behaviour. The photocatalytic activity was evaluated through the degradation of methyl orange (MO) in aqueous solution using a Xe lamp that simulates solar radiation. The photocatalytic activity depends on the dopant amount. The dopant creates levels within the band gap that improving the charge separation, and reduces the recombination e −/h + pairs. The best results of MO degradation were obtained for the films sintered at 450 °C for 90 min and doped with 3 % of Ca2+.

A simple three step method for selective placement of organic groups in mesoporous silica thin films

Selective functionalization of mesoporous silica thin films was achieved using a three step method. The first step consists in an outer surface functionalization, followed by washing off the structuring agent (second step), leaving the inner surface of the pores free to be functionalized in the third step. This reproducible method permits to anchor a volatile silane group in the outer film surface, and a second type of silane group in the inner surface of the pores. As a concept test we modified the outer surface of a mesoporous silica film with trimethylsilane (–Si–(CH3)3) groups and the inner pore surface with propylamino (–Si–(CH2)3–NH2) groups. The obtained silica films were characterized by Environmental Ellipsometric Porosimetry (EEP), EDS, XPS, contact angle and electron microscopy. The selectively functionalized silica (SF) shows an amount of surface amino functions 4.3 times lower than the one-step functionalized (OSF) silica samples. The method presented here can be extended to a combination of silane chlorides and alkoxides as functional groups, opening up a new route toward the synthesis of multifunctional mesoporous thin films with precisely localized organic functions.

Porous inorganic thin films from bridged silsesquioxane sol–gel precursors

A sol–gel process was exploited to produce porous inorganic thin films from phenyl-bridged silsesquioxanes. The evolution of both structural and optical properties of the starting hybrid sol–gel films were monitored, during synthesis and successive thermal curing steps, by Fourier transform infrared (FT-IR) spectroscopy, differential thermal analysis (DTA), thermogravimetric analysis (TGA) and spectroscopic ellipsometry (SE). Involved chemical species, structural and chemical modifications were identified when thermal treatments at increasing temperatures in the range of 60–800°C were applied to the hybrid films. The progressive formation of a crosslinked silica network, template elimination and film densification were observed, resulting in completely inorganic porous thin films of low refractive index. The distinctiveness of this system directly comes from the extremely controlled and uniform dispersion of the porogen at a molecular level, which is intrinsic to the bridged silsesquioxane precursor choice. A quantitative porosity analysis was performed by environmental ellipsometric porosimetry (EEP), studying inorganic film optical and mechanical properties under different relative humidity conditions. A transmission electron microscopy (TEM) in-situ characterization of porosity size and distribution confirms the presence of a spatially structured organization of pores of a few nanometers in diameter.

Understanding the sensing mechanism of polyaniline resistive sensors. Effect of humidity on sensing of organic volatiles

Polyaniline (PANI) is the oldest and potentially one of the most useful conducting polymers. Among other technological applications, PANI films have been extensively used as resistive sensors of volatile analytes. However, at present the mechanism underlying the resistivity changes of the films upon exposure to volatile substances is still unclear. In this work, we investigate different effects of the volatile absorption which can cause the changes polymer electrical resistance when it acts as resistive sensor. This model takes into account three major components: (i) changes in the electronic structure of the polymeric chains (ΔRele), (ii) variations in the electron hopping process (ΔRhop) and (iii) changes in the ionic conductivity between chains due to changes in the dielectric medium between them (ΔRmed). Using two point probe resistivity, UV–visible spectroscopy, environmental ellipsometric porosimetry and atomic force microscopy we study the effect of volatiles on polyaniline films properties to improve the understanding on the mechanism of resistivity changes. Specifically, in the case of water absorption, the resistivity changes seem to be associated with dielectric medium changes and swelling effects (in the high humidity range). It is found that ambient humidity not only gives a resistive signal but also strongly affect the sensing of other volatiles (e.g. ethanol).

Synthesis and photocatalytic characterisation of mesoporous TiO2 films doped with Ca, W and N

Mesoporous TiO2 films doped with Ca2+, W6+ and nitrogen were obtained by sol-gel method using dip-coating procedure onto glass-slides in order to study the influence of dopants in their textural properties and photocatalytic activity. Titania sols were synthesized with and without dopants using titanium isopropoxide as titanium precursor, two complexing agents, acetic acid and acetyl acetone, and two pore generating agents, Pluronic F-127 (F127) and polyethylene glycol hexadecyl ether (Brij58). Films were characterised by Fourier Transform Infrared Spectroscopy (FTIR), Grazing X-ray diffraction (GXRD) and Transmission Electron Microscopy (TEM). Environmental Ellipsometric Porosimetry (EEP) permitted to obtain the adsorption/desorption isotherms and total pore volume, and to determine the porous size distribution and specific surface area (Ss) of the films. The photocatalytic activity was evaluated through the degradation of methyl orange (MO) in aqueous solution under UV light exposure. The photocatalytic activity depends on the nature of dopants, which affect the TiO2-anatase crystallite size and the textural properties of the final material. The best results of MO degradation were obtained for the films doped with Ca2+, this being correlated with the pore size and specific surface area of the films besides the dopant-effect on the photocatalytic mechanisms.

Substrate effect on the swelling and water sorption of Nafion nanomembranes

Swelling and sorption of water, from the vapour phase, by thin (100–1000nm) and ultra-thin (<100nm) Nafion nanomembranes deposited on several surfaces were determined using quartz crystal micro-balance and environmental ellipsometric porosimetry techniques. The water uptake at room temperature, measured as the number of water molecules per ionic group in the polymer, is much lower than that observed in bulky Nafion 117 membranes. Water sorption by supported nanofilms was found to be independent of film thickness, but it depends on substrate nature. Aging due to slow relaxation of the polymer microstructure is also discussed. Results are relevant for modelling the three-phase region of proton exchange membrane fuel cells, where a thin Nafion film covers the carbon supported catalyst nanoparticles.

Green Microwave Synthesis of MIL‐100(Al, Cr, Fe) Nanoparticles for Thin‐Film Elaboration

AbstractNanoparticles of mesoporous MIL‐100(Al, Cr or Fe) metal–organic frameworks were synthesized by a microwave‐assisted solvothermal route with green solvents. The optimization of yield, crystallinity, and particle size was achieved through the control of synthetic parameters such as temperature, heating rate, and dwelling time. The particle size strongly depends on the metallic cation and the metal and linker precursors; nanoparticles smaller than 100 nm were obtained for iron and chromium based MIL‐100. Finally, stable colloidal solutions of iron and chromium MIL‐100 nanoparticles were used for thin layer dip‐coating deposition, which resulted in high optical quality thin films, the porosity of which was investigated by environmental ellipsometric porosimetry.

Love Wave Characterization of the Shear Modulus Variations of Mesoporous Sensitive Films During Vapor Sorption

Anomalous responses of acoustic humidity sensors coated with mesoporous titania sensitive films have been observed at high humidity levels, due to capillary contraction that alters the film mechanical behavior. As the methods commonly used to assess the elasticity of thin films are difficult to apply during sorption, a dedicated method for the characterization of the variations of the elastic shear modulus of thin films under humidity exposure has been developed. The method combines a Love wave platform with environmental ellipsometric porosimetry (EEP). In the presented approach, EEP measures the thickness of the film and the adsorbed humidity volume fraction under vapor exposure, while the Love wave platform provides the phase velocity shifts induced by water sorption. These parameters then feed an accurate model of Love wave propagation in the multilayered platform for the derivation of the shear modulus of the sensitive film. The method was applied to 100 ± 10 nm thick mesoporous titania films, with 25 ± 1% porosity, under relative humidity exposure in the 3%-95% range. It successfully determined decreases of 39% and 67% of the shear modulus during adsorption and desorption, respectively, from a 3.1 GPa initial value.

Sorption and optical properties of sol–gel thin films measured by X-Ray Reflectometry and Ellipsometric Porosimetry

Oxide thin films synthesized using the sol–gel technique have the advantages of low cost, high thickness control, tunable refractive index and silicon technology compatibility, properties that make them potential materials for optoelectronic applications. For very thin films with low porosity, the determination of sorption and optical properties is quite complex because of the small sample size. Thus, there is a need to use especially designed techniques to obtain reliable results. In this work, a comprehensive study on the porosity evolution of SiO2 and TiO2 thin films using X-Ray Reflectometry and Environmental Ellipsometric Porosimetry is presented. For sol–gel SiO2 thin films, it was found that the effective refractive index increases with thermal treatment as the porosity decreases. However, the refractive index of the walls was found constant. For sol–gel TiO2 films, crystallized in anatase phase, both the effective refractive index and the wall refractive index increase with thermal treatment. SiO2 and TiO2 thermal oxides were also characterized for comparison.

Hybrid silica coatings on polycarbonate: enhanced properties

Hybrid silica coatings based on 3- glycidoxypropyltriethoxysilane (GPTES), tetraethylorthosilicate (TEOS) and colloidal silica were deposited on polycarbonate (PC) by the sol–gel method, in order to obtain a material with enhanced properties with respect to raw PC (mainly scratch resistance, hydrophobicity and density), and consequently reach increased durability. The necessity of performing a N2-plasma treatment on PC (before coating deposition) was highlighted in order to obtain a good adherence between the coating and the substrate: XPS measurements showed that after treatment, nitrogenous radicals had formed on the PC surface and were able to link covalently with the sol during its deposition. Adherence was also higher when young sols (<8-day-old) were used. Different alkoxysilanes/colloidal silica ratios were tested to optimize the coating resistance: crack resistance of the coatings was found to be greater when the ratio was high. Scratch resistance of raw PC was enhanced as soon as PC was coated, irrespective of the alkoxysilanes/colloidal silica ratio or the sol ageing time. The density of the coatings was assessed by environmental ellipsometric porosimetry and found to be very high. Water contact angle measurements showed that the hydrophobicity of the coatings was inferior to raw PC. The addition in the sol of a small wt% of octyltriethoxysilane (OTES), 1H,1H,2H,2H-perfluorooctyltriethoxysilane (FTES) and silicone surface additive (BYK-306) allowed a significant increase in hydrophobicity of the samples.

Characterization of Nanoporous Polystyrene Thin Films by Environmental Ellipsometric Porosimetry

Environmental ellipsometric porosimetry (EEP) was used to characterize nanoporous polystyrene thin films containing cylindrical channels oriented perpendicularly to the surface of the film. These samples were prepared from the selective etching of polylactide from a self-assembled polystyrene–polylactide block copolymer. Isopropanol adsorption–desorption isotherms were obtained from the refractive index variations induced by the adsorption and condensation in the pores. Mean pore size and pore-size distributions were consistent with the values obtained by AFM, SEM, and GI-SAXS. More detailed analysis of the EEP data revealed that the topology of the porous structure was more tortuous than the simple picture of vertically oriented nanochannels might suggest. This was confirmed by preparing inorganic replicas that provided a hard negative copy of the porous network of the film. Microscopy on these replicas confirmed that a fraction of the channels exhibited a U-shape and thus were not perfectly perpendicula...

NbVO5 Mesoporous Thin Films by Evaporation Induced Micelles Packing: Pore Size Dependence of the Mechanical Stability upon Thermal Treatment and Li Insertion/Extraction

Mesoporous thin films (MTFs) appear as an interesting architecture for positive electrodes in Li-ion energy storage systems because they offer high specific area and interconnected porosity presenting homogeneous pore size and wall thickness. However, it must be ascertained that the mesostructure survives template removal or/and crystallization and is retained on electrochemical cycling. In order to investigate the potentialities and limits of the soft-templating approach in the case of complex transition metal oxide networks, we deliberately selected a “difficult” compound: NbVO5 was chosen because it combines a challenging synthesis with reported severe structural distortions during the first lithium insertion in the bulk material. In this work, NbVO5 MTFs with different pore sizes were synthesized using the evaporation induced micelles packing (EIMP) method. PS-b-PEO diblock copolymers of different molar weights were used as structure directing agent in order to obtain wormlike porous networks with pore size and wall thickness ranging from 15 to 100 nm. Thermal ellipsometry analysis, used to track surfactant removal and crystallization of the layer, reveals that partial crystallization is possible while retaining the mesoporous architecture. Electron tomography complements result from environmental ellipsometric porosimetry, atomic force microscopy, and transmission electron microscopy to provide a comprehensive description of the structure. A multilayer process is also proposed to build crack-free thick mesoporous films. The mechanical stability of MTFs presenting three different pore sizes is tested by inserting Li+ in amorphous NbVO5 MTFs using cyclic voltammetry. Capacity retention data show that the mechanical stresses associated with Li+ insertion are better accommodated by MTFs compared to nonporous films, and this ability is enhanced as the pore size decreases.

Photocatalytic oxidation of methyl ethyl ketones over sol–gel mesoporous and meso-structured TiO2 films obtained by EISA method

This work reports the influence of the meso-structure of TiO2 films in the photocatalytic oxidation of methyl ethyl ketone. Five types of TiO2 films were prepared combining the sol–gel route with the Evaporation Induced Self-Assembly (EISA) method. Sols were prepared from titanium tetrachloride (TiCl4) using different types of pore generating agents. Films characterisation was performed by Fourier Transform Infrared Spectroscopy (FTIR), Grazing X-ray diffraction (GXRD), X-ray diffraction of small angle and Transmission Electron Microscopy (FE-SEM). Environmental Ellipsometric Porosimetry (EEP) studies were performed to obtain the adsorption/desorption isotherms and calculate porous size distribution, pore volume and specific surface area (Ss) of the films. Kinetic of MEK photocatalytic oxidation data were modelled by Langmuir–Hinshelwood equation and the adsorption and kinetics constants (k and K) were calculated. Better results of MEK degradation were obtained for the Brij58 films deposited at relative humidity (RH) of 20% and 50%. The results are correlated with the porosity properties of the films.

Nanostructured Hybrid Solar Cells Based on Self-Assembled Mesoporous Titania Thin Films

Nanocrystalline mesostructured porous titania thin films with optimized coating and thermal curing conditions have been prepared for the first time using spin-coating deposition technique. The X-ray diffraction (XRD) and the grazing incidence small-angle X-ray scattering (GI-SAXS) measurements revealed that the crystallization and diffuse sintering of amorphous TiO2 into anatase are simultaneously starting between 400 and 500 °C curing temperature, leading to a gridlike open-pore-shape transformation. The environmental ellipsometric porosimetry (EEP) measurements show that the 550 °C-cured TiO2 films exhibit a high porous volume (0.30 cm3 g-1), a large surface area (172 m2 cm-3), and a Young modulus of 1.05 GPa. All solid-state dye-sensitized solar cells (DSSC) based on nanocrystalline mesostructured TiO2 films and poly(3-octylthiophene) as hole conductor allow reproducible achievement of energy conversion efficiencies of about 0.52%. These values, obtained with thin TiO2 films (250 nm), are very promising.

Optimised photocatalytic activity of grid-like mesoporous TiO2films: effect of crystallinity, pore size distribution, and pore accessibility

Photocatalytic activity of anatase cubic-based ordered mesoporous thin films was related to the morphology of the crystalline porous network obtained upon thermal treatment with a specific incremented sequence. The porosity and pore size distribution of these thin films were investigated with a novel Environmental Ellipsometric Porosimetry (EEP) technique. Network crystallinity was assessed by XRD. In parallel, the evolution of the photocatalytic activity was studied through UV-induced photodegradation of methylene blue and lauric acid within the films at the various steps of the temperature treatment. The photoactivity was linked to the porous characteristics of the films and we concluded that the activity is optimal when the porosity is high and completely accessible, and when the nanoparticle and pore size have dimensions of 7.5 and 5.5 nm respectively. Such an optimal system was obtained after a sequential thermal treatment ending with 10 min at 600 °C in air, for which the films adopts an ordered bidirectional grid-like structure.